Highly filled polymer compositions

ABSTRACT

This invention pertains to highly filled polymer compositions comprising a low molecular weight ethylene and/or alpha olefin homopolymers and copolymers, or blends therefrom, filled with high concentrations of fillers or additives. Examples of such fillers or additives include fire retardants, talc, ceramic manufacturing agents, color concentrates, crosslinking agents, and blowing agents. Because of the low crystallinity (and therefore high percentage of amorphous phase) and low viscosities of the base polymers, highly processable compositions can be formed containing even if containing relatively high loadings of fillers or additives. Such highly filled compositions are thus ideally suited as concentrates or masterbatch formulations for a variety of different compounding applications.

This invention pertains to polymer compositions comprising a lowmolecular weight ethylene and/or alpha olefin homopolymer or copolymer,or blends therefrom, which are filled with high concentrations offillers or additives. Examples of such fillers or additives include fireretardants, talc, ceramic manufacturing agents, color concentrates,crosslinking agents, and blowing agents. Because of the lowcrystallinity and low viscosities of the base polymers, highlyprocessable compositions can be formed even when containing relativelyhigh loadings of fillers or additives. Such highly filled compositionsare thus ideally suited as concentrates or masterbatch formulations fora variety of different compounding applications.

Additives in polymer composition are used to modify the properties ofthe bulk polymer for a large number of applications. For instance,fillers are frequently used to improve the stiffness of polymercompositions, or to decrease the coefficient of linear thermalexpansion, or to decrease the overall cost of the polymer composition.However, such fillers are well known to simultaneously decrease impactperformance or toughness of the resultant composition. For example,Joseph A. Randosta & Nikhil C. Trivedi (in Talc, published in Handbookof Fillers and Reinforcements for Plastics, p 160, Harry S. Katz & JohnV. Milewski eds. Van Nostrand Reinhold Co., New York 1978), disclosethat the impact performance of polymeric materials is generallydecreased by the presence of rigid fillers, especially below the glasstransition temperature (Tg) of the matrix material, due to the fillersaction as a “stress concentrator”.

For many applications, the filler is typically incorporated into thebulk polymer at levels ranging from 1 to 50 weight percent of theformulation, depending upon the filler density. Typical thermoplasticformulations (for example, polypropylene, an elastomeric rubber andtalc), even at filler loadings of about 20 percent, have very poorimpact performance and do not function well in uses such as automotivefacia.

U.S. Pat. No. 5,576,374 discloses filled thermoplastic olefiniccompositions which have good low temperature impact performance andmodulus comprising a thermoplastic resin, at least one substantiallylinear ethylene/α-olefin interpolymer, and at least one filler. Thefilled thermoplastic olefinic compositions are said to be useful asautomotive bumpers, facia, wheel covers and grilles and freezercontainers.

Fillers or additives are typically introduced into the bulk polymer byway of a masterbatch, and further improvements in filler or additiveperformance as well as cost improvements could be derived from the useof masterbatches containing higher loadings of the filler or additive.Also improved dispersion of the additive or filler in the bulk resin, aswell as lower compounding and let down energy costs, could be derived ifsuch a high filled polymer masterbatch would also be more processable.

In one aspect, the present invention relates to a filled compositioncomprising one or more homogeneous, low crystallinity, low viscosityethylene/alpha olefin polymers (or blends therefrom) used as the basepolymer, and a high concentration of one or more fillers or additives.The excellent processability of these highly filled compositions iscomparable to that of many non-filled bulk resins used in industrialapplications and therefore they can be co-extruded with good dispersion.

In another aspect, the present invention relates to a fabricated articlecomprising such a highly filled polymer composition.

In yet another aspect, the present invention relates to a multilayeredstructure wherein at least one layer comprises such a filled polymercomposition.

DEFINITIONS

The terms “additive” and “filler” are used interchangeably herein.

The term “base polymer” as used herein means the polymer compositioninto which a filler or additive is mixed during the preliminarycompounding step to form the highly filled polymer compositions of thepresent invention.

The term “masterbatch” is used herein interchangeably with the term“highly filled polymer composition” and means a mixture of the basepolymer and a high concentration of additive or filler.

The term “bulk polymer” as used herein is the resin with which thehighly filled polymer compositions of the present invention are mixed toform a final resin formulation.

The term “compounding step” as used herein means the processing stepduring which the base polymer and the additive or filler are mixed toform the highly filled polymer compositions of the present invention.

The term “let down” as used herein means the processing step duringwhich the highly filled polymer composition of the present invention andthe bulk polymer are mixed to form the final resin formulation.

The term “interpolymer” is used herein to indicate a polymer wherein atleast two different monomers are polymerized to make the interpolymer.

The term “homogeneous polymer” means that in an ethylene/α-olefininterpolymer (1) the α-olefin comonomer is randomly distributed within agiven polymer molecule, (2) substantially all of the polymer moleculeshave the same ethylene-to-comonomer ratio, and (3) the interpolymeressentially lacks a measurable high density (crystalline) polymerfraction as measured by known fractionation techniques such as, forexample, a method that involves polymer fractional elutions as afunction of temperature. Examples of homogeneous polymers include thesubstantially linear polymers defined as in U.S. Pat. No. 5,272,236 (Laiet al.), in U.S. Pat. No. 5,278,272, U.S. Pat. No. 6,054,544 and U.S.Pat. No. 6,335,410 B1.

Fillers, including those used as active and passive flame retardantadditives (aluminum trihydrate, magnesium hydroxide, and calciumcarbonate) when incorporated into polymers significantly lower theirprocessability. For flame retardant applications, such as those meetingUL-94 (V-0), filler levels of 50-65 wt. percent are required, dependingon such parameters as the choice of base resin. Such high levels offiller in a bulk polymer are more accurately introduced using a highlyfilled polymer composition comprising an additive and a base polymer,which may or may not be the same polymer as the bulk polymer. Such ahighly filled composition is often known as a “masterbatch”. The term“masterbatch” as used herein, means a mixture which is mixed orcompounded such that it contains a high filler or additiveconcentration, for example mixtures of a polymer and a highconcentration of carbon black, or a color pigment or a flame retardant.This masterbatch, which is thus more accurately metered than the filleror additive itself, is then used to aportion said filler or additiveaccurately into a much larger amount of the bulk plastic, rubber orelastomer. This subsequent extrusion or other mixing process is known asthe “let down process”.

The composition of the masterbatch is crucial in that its use mustresult, not only in accurate metering of the additive into the bulkpolymer, but also good dispersion of the filler or additive throughoutthe final polymer composition. It is also important that the masterbatchnot only comprise a high concentration of additive, but also that it beeasily processable not only during the mixing process with the bulkpolymer (the let down process) but also during the actual mixing processof the additive and base polymers, that is, the compounding step.

Typically, filler contents significantly in excess of 70 wt. percent arerequired to make filler masterbatches which can be let down to a finalcontent of 50 wt. percent filler along with appropriate bulk resins forspecific applications. The amount of filler that can incorporated intothe polymer is limited only by the molecular structure of thefiller-containing composition and/or the extent that the filler does notinterfere with the other enhancements brought by the polymer. Forinstance, a typical binder for injection molding ceramics can acceptabout 50 percent by weight solids. This loading should be as high aspossible to minimize shrinking, and the higher the better. Similarly,carbon black is a difficult filler/color additive to blend in at orabove 50 percent by weight solids level. The upper limit for filler oradditive loading is determined by the engineer's ability to process thefilled material.

Filler contents greater than 70 wt. percent are generally difficult toprepare owing to the low processability of the system, the compatibilityof the filler with the chosen polymer carrier, and the subsequentphysical integrity of pellets made with high filler content systems.

We have surprisingly found that the low crystallinities and lowviscosities of certain base polymers allow them to be loaded with highlevels of fillers or additives (for example, talc, carbon black, silica,magnesium hydroxide, calcium carbonate, aluminum trihydrate,antioxidants for example, Irganox 1010, a hindered phenolic; Irgafos168, a phosphite; etc., cling additives (for example, polyisobutylene),antiblock additives, colorants, pigments, waxes, nucleating agents,extender oils, flame retardants, and tackifers.

In addition, the compositions of the present invention combine highfiller concentrations with good processability. Solids levels of 70 wtpercent, 80 wt percent or more based on the combined weight of thecomposition and filler may be achieved and the materials are processableduring the extrusion process at torque levels and/or melt temperaturesbelow those observed for compositions of the same filler content butcomprising base resins other than those used in the present invention.

Base Polymer Component

The homogeneous low crystallinity, low viscosity ethylene and/or alphaolefin homopolymers or interpolymers used as the base polymer for thefilled compositions of the present invention may be interpolymers ofethylene and at least one suitable comonomer. Preferred comonomersinclude C₃₋₂₀ α-olefins (especially propylene, isobutylene, 1-butene,1-pentene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene,and 1-octene), C₄₋₄₀ non-conjugated dienes, styrene, alkyl-substitutedstyrene, tetrafluoroethylene, vinylbenzocyclobutene, 1,4-hexadiene,naphthenics (for example, cyclopentene, cyclohexene and cyclooctene),and mixtures thereof. Most preferred are propylene and 1-octene.

The polymers may also be C₃-C₂₀ alpha olefin homopolymers or copolymerssuch as polypropylene, or propylene/ethylene, or propylene C₄-C₂₀alpha-olefin copolymers.

When ethylene propylene diene terpolymers (EPDM's) are prepared, thedienes are typically non-conjugated dienes having from 6 to 15 carbonatoms. Representative examples of suitable non-conjugated dienes thatmay be used to prepare the terpolymers include:

-   (a) Straight chain acyclic dienes such as 1,4-hexadiene;    1,5-heptadiene; and 1,6-octadiene;-   (b) Branched chain acyclic dienes such as 5-methyl-1,4-hexadiene;    3,7-dimethyl-1,6-octadiene; and 3,7-dimethyl-1,7-octadiene;-   (c) Single ring alicyclic dienes such as 4-vinylcyclohexene;    1-allyl-4-isopropylidene cyclohexane; 3-allylcyclopentene;    4-allylcyclohexene; and 1-isopropenyl-4-butenylcyclohexene;-   (d) Multi-ring alicyclic fused and bridged ring dienes such as    dicyclopentadiene; alkenyl, alkylidene, cycloalkenyl, and    cycloalkylidene norbornenes, such as 5-methylene-2-norbornene;    5-methylene-6-methyl-2-norbornene;    5-methylene-6,6-dimethyl-2-norbornene; 5-propenyl-2-norbornene;    5-(3-cyclopentenyl)-2-norbornene; 5-ethylidene-2-norbornene;    5-cyclohexylidene-2-norbornene; etc.

The preferred dienes are selected from the group consisting of1,4-hexadiene; dicyclopentadiene; 5-ethylidene-2-norbornene;5-methylene-2-norbornene; 7-methyl-1,6 octadiene; 4-vinylcyclohexene;etc. One preferred conjugated diene which may be employed is piperylene.

Most preferred monomers are ethylene, mixtures of ethylene, propyleneand ethylidenenorbornene, or mixtures of ethylene and a C₃₋₈ α-olefin,and most especially propylene and 1-octene.

The homogeneous, low crystallinity, low viscosity ethylene/alpha olefinpolymers used as the base polymer for the filled compositions of thepresent invention, may be prepared using the constrained geometrycatalysts disclosed in U.S. Pat. No. 5,064,802, No. 5,132,380, No.5,703,187, No. 6,034,021, EP 0 468 651, EP 0 514 828, WO 93/19104, andWO 95/00526. Another suitable class of catalysts is the metallocenecatalysts disclosed in U.S. Pat. No. 5,044,438; No. 5,057,475; No.5,096,867; and No. 5,324,800. It is noted that constrained geometrycatalysts may be considered as metallocene catalysts, and both aresometimes referred to in the art as single-site catalysts.

For example, catalysts may be selected from the metal coordinationcomplexes corresponding to the formula:

wherein: M is a metal of group 3, 4-10, or the lanthanide series of theperiodic table of the elements; Cp* is a cyclopentadienyl or substitutedcyclopentadienyl group bound in an η⁵ bonding mode to M; Z is a moietycomprising boron, or a member of group 14 of the periodic table of theelements, and optionally sulfur or oxygen, the moiety having up to 40non-hydrogen atoms, and optionally Cp* and Z together form a fused ringsystem; X independently each occurrence is an anionic ligand group, saidX having up to 30 non-hydrogen atoms; n is 2 less than the valence of Mwhen Y is anionic, or 1 less than the valence of M when Y is neutral; Lindependently each occurrence is a neutral Lewis base ligand group, saidL having up to 30 non-hydrogen atoms; m is 0,1, 2, 3, or 4; and Y is ananionic or neutral ligand group bonded to Z and M comprising nitrogen,phosphorus, oxygen or sulfur and having up to 40 non-hydrogen atoms,optionally Y and Z together form a fused ring system.

Suitable catalysts may also be selected from the metal coordinationcomplex corresponds to the formula:

wherein R′ each occurrence is independently selected from the groupconsisting of hydrogen, alkyl, aryl, silyl, germyl, cyano, halo andcombinations thereof having up to 20 non-hydrogen atoms; X eachoccurrence independently is selected from the group consisting ofhydride, halo, alkyl, aryl, silyl, germyl, aryloxy, alkoxy, amide,siloxy, and combinations thereof having up to 20 non-hydrogen atoms; Lindependently each occurrence is a neural Lewis base ligand having up to30 non-hydrogen atoms; Y is —O—, —S—, —NR*—, —PR*—, or a neutral twoelectron donor ligand selected from the group consisting of OR*, SR*,NR*₂, PR*₂; M, n, and m are as previously defined; and Z is SIR*₂, CR*₂,SiR*₂SiR*₂, CR*₂CR*₂, CR*═CR*, CR*₂SiR*₂, GeR*₂, BR*, BR*₂; wherein: R*each occurrence is independently selected from the group consisting ofhydrogen, alkyl, aryl, silyl, halogenated alkyl, halogenated aryl groupshaving up to 20 non-hydrogen atoms, and mixtures thereof, or two or moreR* groups from Y, Z, or both Y and Z form a fused ring system.

It should be noted that whereas formula I and the following formulasindicate a monomeric structure for the catalysts, the complex may existas a dimer or higher oligomer.

Further preferably, at least one of R′, Z, or R* is an electron donatingmoiety. Thus, highly preferably Y is a nitrogen or phosphorus containinggroup corresponding to the formula —N(R″″)—or —P(R″″)—, wherein R″″ isC₁₋₁₀ alkyl or aryl, that is, an amido or phosphido group.

Additional catalysts may be selected from the amidosilane- oramidoalkanediyl-compounds corresponding to the formula:

wherein: M is titanium, zirconium or hafnium, bound in an η⁵ bondingmode to the cyclopentadienyl group; R′ each occurrence is independentlyselected from the group consisting of hydrogen, silyl, alkyl, aryl andcombinations thereof having up to 10 carbon or silicon atoms; E issilicon or carbon; X independently each occurrence is hydride, halo,alkyl, aryl, aryloxy or alkoxy of up to 10 carbons; m is 1 or 2; and nis 1 or 2 depending on the valence of M.

Examples of the above metal coordination compounds include, but are notlimited to, compounds in which the R′ on the amido group is methyl,ethyl, propyl, butyl, pentyl, hexyl, (including isomers), norbornyl,benzyl, phenyl, etc.; the cyclopentadienyl group is cyclopentadienyl,indenyl, tetrahydroindenyl, fluorenyl, octahydrofluorenyl, etc.; R′ onthe foregoing cyclopentadienyl groups each occurrence is hydrogen,methyl, ethyl, propyl, butyl, pentyl, hexyl, (including isomers),norbornyl, benzyl, phenyl, etc.; and X is chloro, bromo, iodo, methyl,ethyl, propyl, butyl, pentyl, hexyl, (including isomers), norbornyl,benzyl, phenyl, etc.

Specific compounds include, but are not limited to,(tertbutylamido)(tetramethyl-η⁵-cyclopentadienyl)-1,2-ethanediylzirconiumdimethyl, (tert-butylamido)(tetramethyl-η⁵-cyclo pentadienyl)-1,2-ethanediyltitanium dimethyl,(methylamido)(tetramethyl-η⁵-cyclopenta dienyl)-1,2-ethanediylzirconiumdichloride, (methylamido)(tetramethyl-η⁵-eyelopenta dienyl)-1,2-ethanediyltitanium dichloride,(ethylamido)(tetramethyl-η⁵-cyclopentadienyl)-methylenetitaniumdichloro,(tertbutylamido)diphenyl(tetramethyl-η⁵-cyclopentadienyl)-silanezirconium dibenzyl,(benzylamido)dimethyl-(tetramethyl-η⁵cyclopentadienyl)ilanetitaniumdichloride,and phenylphosphido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanezirconium dibenzyl. Another suitable class of catalysts is substitutedindenyl containing metal complexes as disclosed in U.S. Pat. No.5,965,756 and No. 6,015,868. Other preferred catalysts are disclosed inU.S. Pat. No. 5,616,664 and publications U.S. Pat. No. 6,268,444; U.S.Pat. No. 6,515,155; U.S. Pat. No. 6,613,921; and WO 01/042315A1. Thesecatalysts tend to have a higher molecular weight capability.

One class of the above catalysts is the indenyl containing metalwherein:

M is titanium, zirconium or hafnium in the +2, +3 or +4 formal oxidationstate;

A′ is a substituted indenyl group substituted in at least the 2 or 3position with a group selected from hydrocarbyl, fluoro-substitutedhydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl,dialkylamino-substituted hydrocarbyl, silyl, germyl and mixturesthereof, the group containing up to 40 non-hydrogen atoms, and the A′further being covalently bonded to M by means of a divalent Z group; Zis a divalent moiety bound to both A′ and M via σ-bonds, the Zcomprising boron, or a member of Group 14 of the Periodic Table of theElements, and also comprising nitrogen, phosphorus, sulphur or oxygen; Xis an anionic or dianionic ligand group having up to 60 atoms exclusiveof the class of ligands that are cyclic, delocalized, π-bound ligandgroups; X′ independently each occurrence is a neutral Lewis base, havingup to 20 atoms; p is 0, 1 or 2, and is two less than the formaloxidation state of M, with the proviso that when X is a dianionic ligandgroup, p is 1; and q is 0, 1 or 2.

The above complexes may exist as isolated crystals optionally in pureform or as a mixture with other complexes, in the form of a solvatedadduct, optionally in a solvent, especially an organic liquid, as wellas in the form of a dimer or chelated derivative thereof, wherein thechelating agent is an organic material, preferably a neutral Lewis base,especially a trihydrocarbylamine, trihydrocarbylphosphine, orhalogenated derivative thereof.

Preferred catalysts are complexes corresponding to the formula:

wherein R₁ and R₂ independently are groups selected from hydrogen,hydrocarbyl, perfluoro substituted hydrocarbyl, silyl, germyl andmixtures thereof, the group containing up to 20 non-hydrogen atoms, withthe proviso that at least one of R₁ or R₂ is not hydrogen; R₃, R₄, R₅,and R₆ independently are groups selected from hydrogen, hydrocarbyl,perfluoro substituted hydrocarbyl, silyl, germyl and mixtures thereof,the group containing up to 20 non-hydrogen atoms; M is titanium,zirconium or hafnium; Z is a divalent moiety comprising boron, or amember of Group 14 of the Periodic Table of the Elements, and alsocomprising nitrogen, phosphorus, sulfur or oxygen, the moiety having upto 60 non-hydrogen atoms; p is 0, 1 or 2; q is zero or one; with theproviso that: when p is 2, q is zero, M is in the +4 formal oxidationstate, and X is an anionic ligand selected from the group consisting ofhalide, hydrocarbyl, hydrocarbyloxy, di(hydrocarbyl)amido,di(hydrocarbyl)phosphido, hydrocarbyl sulfido, and silyl groups, as wellas halo-, di(hydrocarbyl)amino-, hydrocarbyloxy- anddi(hydrocarbyl)phosphino-substituted derivatives thereof, the X grouphaving up to 20 non-hydrogen atoms, when p is 1, q is zero, M is in the+3 formal oxidation state, and X is a stabilizing anionic ligand groupselected from the group consisting of allyl,2-(N,N-dimethylaminomethyl)phenyl, and 2-(N,N-dimethyl)-aminobenzyl, orM is in the +4 formal oxidation state, and X is a divalent derivative ofa conjugated diene, M and X together forming a metallocyclopentenegroup, and when p is 0, q is 1, M is in the +2 formal oxidation state,and X′ is a neutral, conjugated or non-conjugated diene, optionallysubstituted with one or more hydrocarbyl groups, the X′ having up to 40carbon atoms and forming a π-complex with M.

More preferred catalysts are complexes corresponding to the formula:

wherein: R₁ and R₂ are hydrogen or C₁₋₆ alkyl, with the proviso that atleast one of R₁ or R₂ is not hydrogen; R₃, R₄, R₅, and R₆ independentlyare hydrogen or C₁₋₆ alkyl; M is titanium; Y is —O—,—S—, —NR*—, —PR*—;Z* is SiR*₂, CR*₂, SiR*₂SiR*₂, CR*₂CR*₂, CR*═CR*, CR*₂SiR*₂, or GeR*₂;R* each occurrence is independently hydrogen, or a member selected fromhydrocarbyl, hydrocarbyloxy, silyl, halogenated alkyl, halogenated aryl,and combinations thereof, the R* having up to 20 non-hydrogen atoms, andoptionally, two R* groups from Z (when R* is not hydrogen), or an R*group from Z and an R* group from Y form a ring system; p is 0, 1 or 2;q is zero or one; with the proviso that: when p is 2, q is zero, M is inthe +4 formal oxidation state, and X is independently each occurrencemethyl or benzyl, when p is 1, q is zero, M is in the +3 formaloxidation state, and X is 2-(N,N-dimethyl)aminobenzyl; or M is in the +4formal oxidation state and X is 1,4-butadienyl, and when p is 0, q is 1,M is in the +2 formal oxidation state, and X′ is1,4-diphenyl-1,3-butadiene or 1,3-pentadiene. The latter diene isillustrative of unsymmetrical diene groups that result in production ofmetal complexes that are actually mixtures of the respective geometricalisomers.

Other catalysts, cocatalysts, catalyst systems, and activatingtechniques which may be used in the practice of the invention disclosedherein may include those disclosed in; WO 96/23010, published on Aug. 1,1996, WO 99/14250, published Mar. 25, 1999, WO 98/41529, published Sep.24, 1998, WO 97/42241, published Nov. 13, 1997, WO 97/42241, publishedNov. 13, 1997, those disclosed by Scollard, et al., in J. Am. Chem. Soc1996, 118, 10008-10009, EP 0 468 537 B1, published Nov. 13, 1996, WO97/22635, published Jun. 26, 1997, EP 0 949 278 A2, published Oct. 13,1999; EP 0 949 279 A2, published Oct. 13, 1999; EP 1 063 244 A2,published Dec. 27, 2000; U.S. Pat. No. 5,408,017; U.S. Pat. No.5,767,208; U.S. Pat. No. 5,907,021; WO 88/05792, published Aug. 11,1988; WO 88/05793, published Aug. 11, 1988; WO 93/25590, published Dec.23, 1993;U.S. Pat. No. 5,599,761; U.S. Pat. No. 5,218,071; WO 90/07526,published Jul. 12, 1990; U.S. Pat. No. 5,972,822; U.S. Pat. No.6,074,977; U.S. Pat. No. 6,013,819; U.S. Pat. No. 5,296,433; U.S. Pat.No. 4,874,880; U.S. Pat. No. 5,198,401; U.S. Pat. No. 5,621,127; U.S.Pat. No. 5,703,257; U.S. Pat. No. 5,728,855; U.S. Pat. No. 5,731,253;U.S. Pat. No. 5,710,224; U.S. Pat. No. 5,883,204; U.S. Pat. No.5,504,049; U.S. Pat. No. 5,962,714; U.S. Pat. No. 5,965,677; U.S. Pat.No. 5,427,991; WO 93/21238, published Oct. 28, 1993; WO 94/03506,published Feb. 17, 1994; WO 93/21242, published Oct. 28, 1993; WO94/00500, published Jan. 6, 1994, WO 96/00244, published Jan. 4, 1996,WO 98/50392, published Nov. 12, 1998; Wang, et al., Organometallics1998, 17, 3149-3151; Younkin, et al., Science 2000, 287, 460-462, Chenand Marks, Chem. Rev. 2000, 100, 1391-1434, Alt and Koppl, Chem. Rev.2000, 100, 1205-1221; Resconi, et al., Chem. Rev. 2000, 100, 1253-1345;Ittel, et al., Chem Rev. 2000, 100, 1169-1203; Coates, Chem. Rev., 2000,100, 1223-1251; WO 96/13530, published May 9, 1996. Also useful arethose catalysts, cocatalysts, and catalyst systems disclosed in U.S.Pat. No. 5,965,756; U.S. Pat. No. 6,150,297; and publications U.S. Pat.No. 6,268,444 and U.S. Pat. No. 6,515,155. In addition, methods forpreparing the aforementioned catalysts are described, for example, inU.S. Pat. No. 6,015,868.

The above-described catalysts may be rendered catalytically active bycombination with an activating cocatalyst or by use of an activatingtechnique. Suitable activating cocatalysts for use herein include, butare not limited to, polymeric or oligomeric alumoxanes, especiallymethylalumoxane, triisobutyl aluminum modified methylalumoxane, orisobutylalumoxane; neutral Lewis acids, such as C₁₋₃₀ hydrocarbylsubstituted Group 13 compounds, especially tri(hydrocarbyl)aluminum- ortri(hydrocarbyl)boron compounds and halogenated (includingperhalogenated) derivatives thereof, having from 1 to 30 carbons in eachhydrocarbyl or halogenated hydrocarbyl group, more especiallyperfluorinated tri(aryl)boron and perfluorinated tri(aryl)aluminumcompounds, mixtures of fluoro-substituted(aryl)boron compounds withalkyl-containing aluminum compounds, especially mixtures oftris(pentafluorophenyl)borane with trialkylaluminum or mixtures oftris(pentafluorophenyl)borane with alkylalumoxanes, more especiallymixtures of tris(pentafluorophenyl)borane with methylalumoxane andmixtures of tris(pentafluorophenyl)borane with methylalumoxane modifiedwith a percentage of higher alkyl groups (MMAO), and most especiallytris(pentafluorophenyl)borane and tris(pentafluorophenyl)-aluminum;non-polymeric, compatible, non-coordinating, ion forming compounds(including the use of such compounds under oxidizing conditions),especially the use of ammoniun-, phosphonium-, oxonium-, carbonium-,silylium- or sulfonium- salts of compatible, non-coordinating anions, orferrocenium salts of compatible, non-coordinating anions; bulkelectrolysis and combinations of the foregoing activating cocatalystsand techniques. The foregoing activating cocatalysts and activatingtechniques have been previously taught with respect to different metalcomplexes in the following references: EP-A-277,003, U.S. Pat. No.5,153,157, U.S. Pat. No. 5,064,802, EP-A-468,651 (equivalent to U.S.Ser. No. 07/547,718), EP-A-520,732 (equivalent to U.S. Ser. No.07/876,268), and EP-A-520,732 (equivalent to U.S. Ser. No. 07/884,966filed May 1, 1992).

Combinations of neutral Lewis acids, especially the combination of atrialkyl aluminum compound having from 1 to 4 carbons in each alkylgroup and a halogenated tri(hydrocarbyl)boron compound having from 1 to20 carbons in each hydrocarbyl group, especiallytris(pentafluorophenyl)borane, further combinations of such neutralLewis acid mixtures with a polymeric or oligomeric alumoxane, andcombinations of a single neutral Lewis acid, especiallytris(pentafluorophenyl)borane with a polymeric or oligomeric alumoxaneare especially desirable activating cocatalysts. It has been observedthat the most efficient catalyst activation using such a combination oftris(pentafluoro-phenyl)borane/alumoxane mixture occurs at reducedlevels of alumoxane. Preferred molar ratios of Group 4 metalcomplex:tris(pentafluoro-phenylborane:alumoxane are from 1:1:1 to1:5:10, more preferably from 1:1:1 to 1:3:5. Such efficient use of lowerlevels of alumoxane allows for the production of olefin polymers withhigh catalytic efficiencies using less of the expensive alumoxanecocatalyst. Additionally, polymers with lower levels of aluminumresidue, and hence greater clarity, are obtained.

Suitable ion forming compounds useful as cocatalysts in some embodimentsof the invention comprise a cation which is a Bronsted acid capable ofdonating a proton, and a compatible, non-coordinating anion, A⁻. As usedherein, the term “non-coordinating” means an anion or substance whicheither does not coordinate to the Group 4 metal containing precursorcomplex and the catalytic derivative derived therefrom, or which is onlyweakly coordinated to such complexes thereby remaining sufficientlylabile to be displaced by a neutral Lewis base. A non-coordinating anionspecifically refers to an anion which, when functioning as a chargebalancing anion in a cationic metal complex, does not transfer ananionic substituent or fragment thereof to the cation thereby formingneutral complexes during the time which would substantially interferewith the intended use of the cationic metal complex as a catalyst.“Compatible anions” are anions which are not degraded to neutrality whenthe initially formed complex decomposes and are non-interfering withdesired subsequent polymerization or other uses of the complex.

Preferred anions are those containing a single coordination complexcomprising a charge-bearing metal or metalloid core which anion iscapable of balancing the charge of the active catalyst species (themetal cation) which may be formed when the two components are combined.Also, the anion should be sufficiently labile to be displaced byolefinic, diolefinic and acetylenically unsaturated compounds or otherneutral Lewis bases such as ethers or nitrites. Suitable metals include,but are not limited to, aluminum, gold and platinum. Suitable metalloidsinclude, but are not limited to, boron, phosphorus, and silicon.Compounds containing anions which comprise coordination complexescontaining a single metal or metalloid atom are, of course, known in theart and many, particularly such compounds containing a single boron atomin the anion portion, are available commercially.

Preferably such cocatalysts may be represented by the following generalformula:(L*−H)_(d) ⁺(A)^(d−)  Formula VIIwherein L* is a neutral Lewis base; (L*−H)+ is a Bronsted acid; A^(d−)is an anion having a charge of d−, and d is an integer from 1 to 3. Morepreferably A^(d−) corresponds to the formula: [M′Q₄]⁻, wherein M′ isboron or aluminum in the +3 formal oxidation state; and Q independentlyeach occurrence is selected from hydride, dialkylamido, halide,hydrocarbyl, hydrocarbyloxide, halosubstituted-hydrocarbyl,halosubstituted hydrocarbyloxy, and halo-substituted silylhydrocarbylradicals (including perhalogenated hydrocarbyl-perhalogenatedhydrocarbyloxy- and perhalogenated silylhydrocarbyl radicals), the Qhaving up to 20 carbons with the proviso that in not more than oneoccurrence is Q halide. Examples of suitable hydrocarbyloxide Q groupsare disclosed in U.S. Pat. No. 5,296,433.

In a more preferred embodiment, d is one, that is, the counter ion has asingle negative charge and is A⁻. Activating cocatalysts comprisingboron which are particularly useful in the preparation of catalysts ofthis invention may be represented by the following general formula:(L*−H)⁺(M′Q₄)⁻;   Formula VIIIwherein L* is as previously defined; M′ is boron or aluminum in a formaloxidation state of 3; and Q is a hydrocarbyl-, hydrocarbyloxy-,fluorinated hydrocarbyl-, fluorinated hydrocarbyloxy-, or fluorinatedsilylhydrocarbyl- group of up to 20 non-hydrogen atoms, with the provisothat in not more than one occasion is Q hydrocarbyl. Most preferably, Qin each occurrence is a fluorinated aryl group, especially apentafluorophenyl group. Preferred (L*−H)⁺ cations areN,N-dimethylanilinium, N,N-di(octadecyl)anilinium,di(octadecyl)methylammonium, methylbis(hydrogenated tallowyl)ammonium,and tributylammonium.

Illustrative, but not limiting, examples of boron compounds which may beused as an activating cocatalyst are tri-substituted ammonium salts suchas: trimethylammonium tetrakis(pentafluorophenyl)borate;triethylammonium tetrakis(pentafluorophenyl)borate; tripropylammoniumtetrakis(pentafluorophenyl)borate; tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate; tri(sec-butyl)ammoniumtetrakis(pentafluorophenyl)borate; N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate; N,N-dimethylaniliniumn-butyltris(pentafluorophenyl)borate; N,N-dimethylaniliniumbenzyltris(pentafluorophenyl)borate; N,N-dimethylaniliniumtetrakis(4-(t-butyldimethylsilyl)-2,3,5,6-tetrafluorophenyl)borate;N,N-dimethylaniliniumtetrakis(4-(triisopropylsilyl)-2,3,5,6-tetrafluorophenyl)borate;N,N-dimethylanilinium pentafluoro phenoxytris(pentafluorophenyl)borate;N,N-diethylanilinium tetrakis(pentafluorophenyl)borate;N,N-dimethyl-2,4,6-trimethylanilinium tetrakis(pentafluorophenyl)borate;trimethylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate;triethylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate;tripropylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate;tri(n-butyl)ammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate,dimethyl(t-butyl)ammonium tetrakis(2,3,4,6-tetra fluorophenyl)borate;N,N-dimethylanilinium tetrakis(2,3,4,6-tetrafluorophenyl)borate;N,N-diethylanilinium tetrakis(2,3,4,6-tetrafluorophenyl)borate; andN,N-dimethyl-2,4,6-trimethylaniliniumtetrakis(2,3,4,6-tetrafluorophenyl)borate; dialkyl ammonium salts suchas: di-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate, anddicyclohexylammonium tetrakis(pentafluorophenyl)borate; tri-substitutedphosphonium salts such as: triphenylphosphoniumtetrakis(pentafluorophenyl)borate, tri(o-tolyl)phosphoniumtetrakis(pentafluorophenyl)borate, andtri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate;di-substituted oxonium salts such as: diphenyloxoniumtetrakis(pentafluorophenyl)borate, di(o-tolyl)oxonium tetrakis(pentafluorophenyl)borate, and di(2,6-dimethylphenyl)oxoniumtetrakis(pentafluorophenyl)borate; di-substituted sulfonium salts suchas: diphenylsulfonium tetrakis(pentafluorophenyl)borate,di(o-tolyl)sulfonium tetrakis(pentafluorophenyl)borate, andbis(2,6-dimethylphenyl)sulfonium tetrakis(pentafluorophenyl)borate.

Preferred silylium salt activating cocatalysts include, but are notlimited to, trimethylsilylium tetrakispentafluorophenylborate,triethylsilylium tetrakispentafluorophenylborate and ether substitutedadducts thereof. Silylium salts have been previously genericallydisclosed in J. Chem. Soc. Chem. Comm., 1993, 383-384, as well asLambert, J. B., et al., Organometallics, 1994, 13, 2430-2443. The use ofthe above silylium salts as activating cocatalysts for additionpolymerization catalysts is disclosed in U.S. Pat. No. 5,625,087.Certain complexes of alcohols, mercaptans, silanols, and oximes withtris(pentafluorophenyl)borane are also effective catalyst activators andmay be used in embodiments of the invention. Such cocatalysts aredisclosed in U.S. Pat. No. 5,296,433.

The catalyst system may be prepared as a homogeneous catalyst byaddition of the requisite components to a solvent in whichpolymerization will be carried out by solution polymerizationprocedures. The catalyst system may also be prepared and employed as aheterogeneous catalyst by adsorbing the requisite components on acatalyst support material such as silica gel, alumina or other suitableinorganic support material. When prepared in heterogeneous or supportedform, it is preferred to use silica as the support material.

At all times, the individual ingredients, as well as the catalystcomponents, should be protected from oxygen and moisture. Therefore, thecatalyst components and catalysts should be prepared and recovered in anoxygen and moisture free atmosphere. Preferably, therefore, thereactions are performed in the presence of a dry, inert gas such as, forexample, nitrogen or argon.

The molar ratio of metal complex: activating cocatalyst employedpreferably ranges from 1:1000 to 2:1, more preferably from 1:5 to 1.5:1,most preferably from 1:2 to 1:1. In the preferred case in which a metalcomplex is activated by trispentafluorophenylborane andtriisobutylaluminum modified methylalumoxane, thetitanium:boron:aluminum molar ratio is typically from 1:10:50 to1:0.5:0.1, most typically from 1:3:5.

In general, the polymerization may be accomplished at conditions forZiegler-Natta- or metallocene-type polymerization reactions, that is,reactor pressures ranging from atmospheric to 3500 atmospheres (34.5kPa). The reactor temperature should be greater than 80° C., typicallyfrom 100° C. to 250° C., and preferably from 100° C. to 150° C., withhigher reactor temperatures, that is, reactor temperatures greater than100° C. generally favoring the formation of lower molecular weightpolymers.

Generally the polymerization process is carried out with a differentialpressure of ethylene of from 10 to 1000 psi (70 to 7000 kPa), mostpreferably from 40 to 60 psi (300 to 400 kPa). The polymerization isgenerally conducted at a temperature of from 80 to 250° C., preferablyfrom 90 to 170° C., and most preferably from greater than 95 to 140° C.

In most polymerization reactions the molar ratio ofcatalyst:polymerizable compounds employed is from 10⁻¹²:1 to 10⁻¹:1,more preferably from 10⁻⁹:1 to 10⁻⁵:1.

Solution polymerization conditions utilize a solvent for the respectivecomponents of the reaction. Preferred solvents include mineral oils andthe various hydrocarbons which are liquid at reaction temperatures.Illustrative examples of useful solvents include alkanes such aspentane, isopentane, hexane, heptane, octane and nonane, as well asmixtures of alkanes including kerosene and Isopar E™, available fromExxon Chemicals Inc.; cycloalkanes such as cyclopentane and cyclohexane;and aromatics such as benzene, toluene, xylenes, ethylbenzene anddiethylbenzene.

The solvent will be present in an amount sufficient to prevent phaseseparation in the reactor. As the solvent functions to absorb heat, lesssolvent leads to a less adiabatic reactor. The solvent:ethylene ratio(weight basis) will typically be from 2.5:1 to 12:1, beyond which pointcatalyst efficiency suffers. The most typical solvent:ethylene ratio(weight basis) is in the range of from 5:1 to 10:1.

The polymerization may be carried out as a batchwise or a continuouspolymerization process, with continuous solution polymerizationsprocesses being most preferred for the preparation of the liquid lowmolecular weight polymers of the invention. In a continuous process,ethylene, comonomer, and optionally solvent and diene are continuouslysupplied to the reaction zone and polymer product continuously removedtherefrom.

The homogeneous, low crystallinity, low viscosity ethylene and/or alphaolefin homopolymers and interpolymers used as the base polymer for thefilled compositions of the present invention may be polymerized in afirst reactor, with a second polymer (of higher molecular weight and/orof different density, and/or which is heterogeneous) being polymerizedin a second reactor which is connected in series or in parallel to thatin which the liquid low molecular weight polymer is produced, to preparein-reactor polymer blends having desirable properties. An example of adual reactor process which may be adapted in accordance with theteachings of this disclosure to prepare blends wherein at least onecomponent is the homogeneous liquid low molecular weightethylene/alpha-olefin polymer of this invention, is disclosed in WO94/00500, as well as patent publication WO 94/17112.

The polymer may also be prepared using a dual catalyst system in eithera single, dual or multiple reactor configuration as disclosed incopending U.S. patent application Ser. No. 60/504,412 filed on Sep. 19,2003 in the Teresa Karjala and Brian Kolthammmer.

The homogeneous low crystallinity, low viscosity ethylene and/or alphaolefin homopolymers or interpolymers used as the base polymer for thefilled compositions of the present invention may also be blended withone or more other polymers prior to mixing with the additive. Such otherblend polymers include but are not limited to, styrene block copolymers,rubbers, linear low density polyethylene (LLDPE), high densitypolyethylne (HDPE), low density polyethylene (LDPE), ethylene/vinylacetate (EVA) copolymer, ethylene-carboxylic acid copolymers (EAA),ethylene acrylate copolymers, polybutylene, polybutadiene, nylons,polycarbonates, polyesters, polypropylene, ethylene-propyleneinterpolymers such as ethylene-propylene rubber,ethylene-propylene-diene monomer rubbers, chlorinated polyethylene,thermoplastic vulcanates, ethylene ethylacrylate polymers (EEA),ethylene styrene interpolymers (ESI), polyurethanes, as well asgraft-modified olefin polymers, and combinations of two or more of thesepolymers.

Filler or Additive Component

Preferred inorganic fillers are ionic inorganic materials. Preferredexamples of inorganic fillers are glass fibers, talc, calcium carbonate,alumina trihydrate, glass fibers, marble dust, cement dust, clay,feldspar, silica or glass, fumed silica, alumina, magnesium oxide,magnesium hydroxide, antimony oxide, zinc oxide, barium sulfate,aluminum silicate, calcium silicate, titanium dioxide, titanates, glassmicrospheres or chalk. Of these fillers, barium sulfate, talc, calciumcarbonate, silica/glass, glass fibers, alumina and titanium dioxide, andmixtures thereof are preferred. The most preferred inorganic fillers aretalc, calcium carbonate, barium sulfate, glass fibers or mixturesthereof.

The filled polymer composition of the present invention may contain oneor more organic fillers or additives, for example antioxidants, forexample, hindered phenolics (for example, Irganox™ 1010, Irganox™ 1076),phosphites (for example, Irgafose™ 168); light stabilizers, such ashindered amines; plasticizers, such as dioctylphthalate or epoxidizedsoy bean oil; tackifiers, such as known hydrocarbon tackifiers; waxes,such as polyethylene waxes; processing aids, such as oils, stearic acidor a metal salt thereof; crosslinking agents, such as peroxides orsilanes; colorants or pigments, carbon black, graphite, carbon fibers,and blowing agents, to the extent that they do not interfere withdesired physical properties of the filled polymer composition of thepresent invention.

The concentration of filler in the highly filled compositions of thepresent invention is greater than or equal to 40, preferably greaterthan or equal to 60, even more preferably greater than or equal to 80weight percent (based on the combined weights of base resin and filler).

The total percent crystallinity of the base polymer component of thehighly filled compositions of the present invention is from 0 to 30,preferably from 3 to 25, more preferably from 5 to 20 percent

The viscosity of the base polymer component of the highly filledcompositions of the present invention is from 500 to 50,000, preferablyfrom 2,000 to 30,000, more preferably from 5,000 to 20,000 cP at 350° F.

The density of the base polymer component of the highly filledcompositions of the present invention will typically be from 0.865 g/cm³to 0.885 g/cm³.

The highly filled polymer compositions of the present invention can becompounded by any convenient method, such as dry blending ofinterpolymer(s), the filler(s) and optional additives and subsequentlymelt mixing, either directly in the extruder used to make the finishedarticle, or by pre-melt mixing in a separate extruder (for example, aBanbury mixer). Dry blends of the compositions can also be directlyinjection molded without pre-melt mixture.

In another embodiment of the present invention, the highly filledpolymer compositions may comprise a broad range of temperature sensitivematerials including but not limited to, peroxides, perfumes, andtemperature sensitive pigments. The lower melting temperatures and lowmolecular weights of the polymer component also enables miscibility andcompatibility with many temperature sensitive materials. Suchcombinations are not accessible to carriers of the prior art. Forinstance, the lower melting point of the instantly claimed polymercompositions are approx. 69° C., allowing masterbatches to be formedwith low decomposition temperature peroxides such as Triganox™ 123-C75(a registered trademark and product of Akzo Nobel) which has thefollowing half-life characteristics: 6 mins at 81° C.; 1 hr at 61° C.;and 10 hr 43° C.

In another embodiment of the present invention the instantly claimedpolymer compositions find application in novel die compactiontechnologies (including warm compaction, agglomerated fine powdercompaction and hard material compaction) as well as powder injectionmolding, cold isostatic pressing, powder extrusion, rapid prototyping,freeform fabrication and green machining. Such applications are enabledas a result of the very low viscosities of the polymer compositions ofthe present invention, which are still sufficient to avoid powderseparation. The range of viscosity allows the loaded polymer to formeasily, resulting in consistent mixing and molding conditions. All thisproduces minimal residual stresses, giving less distortion, and improveddimensional precision.

In another embodiment of the present invention, the instantly claimedpolymer compositions find application as a binder and/or carrier ofmagnetic ferrite filler, for use in magnetic freezer closures, or otherarticles which carry a magnetic backing including, but not limited to,paper, labels, business cards, etc. with a magnetic backing. Suchbackings can be applied through a slot-die coater.

In addition to their use as masterbatches, the highly filled polymercompositions of the present invention can be processed directly tofabricated articles by any suitable means known in the art. For example,the filled polymer composition can be processed to films or sheets or toone or more layers of a multilayered structure by know processes, suchas calendering, blown film, casting or (co-)extrusion processes.Injection molded, compression molded, extruded or blow molded parts canalso be prepared from the filled polymer compositions of the presentinvention. Alternatively, the filled polymer compositions can beprocessed to foams or fibers. Useful temperatures for processing theinterpolymer(s) in combination with the filler(s) and optional additivesto the fabricated articles generally are from 100° C. to 300° C.,preferably from 120° C. to 250° C., more preferably from 140° C. to 200°C.

The filled polymer compositions of the present invention can also beextruded onto a substrate. Alternatively the filled polymer compositionsof the present invention can be extruded, milled, or calendered asunsupported films or sheets, for example for producing floor tiles, walltiles, floor sheeting, wall coverings, or ceiling coverings. As suchthey are particularly useful as sound insulating or energy absorbinglayers, films, sheets or boards. Films, sheets or boards of a widethickness range can be produced. Depending on the intended end-use,useful thicknesses generally are from 0.5 to 20 mm, preferably from 1 to10 mm. Alternatively, injection molded parts or blow molded articles,such as toys, containers, building and construction materials,automotive components, and other durable goods can be produced from thefilled polymer compositions of the present invention.

The skilled artisan will appreciate that the invention disclosed hereinmay be practiced in the absence of any component which has not beenspecifically disclosed. The following examples are provided as furtherillustration of the invention and are not to be construed as limiting.Unless stated to the contrary all parts and percentages are expressed ona weight basis.

EXAMPLES

Unless indicated otherwise, the following testing procedures are to beemployed:

Melt viscosity is determined in accordance with the following procedureusing a Brookfield Laboratories DVII+ Viscometer in disposable aluminumsample chambers. The spindle used is a SC-31 hot-melt spindle, suitablefor measuring viscosities in the range of from 10 to 100,000 centipoise.The sample was poured in the chamber, which is in turn inserted into aBrookfield Thermosel and locked into place with bent needle-nose pliers.The sample chamber has a notch on the bottom that fits the bottom of theBrookfield Thermosel to ensure that the chamber is not allowed to turnwhen the spindle is inserted and spinning. The sample is heated to therequired temperature with additional sample being added until the meltedsample is about 1 inch below the top of the sample chamber. Theviscometer apparatus is lowered and the spindle submerged into thesample chamber. Lowering is continued until brackets on the viscometeralign on the Thermosel. The viscometer is turned on, and set to a shearrate which leads to a torque reading in the range of 30 to 60 percent.Readings are taken every minute for about 15 minutes, or until thevalues stabilize, at which final reading is recorded.

The density of the polymers used in the present invention, was measuredin accordance with ASTM D-792.

The melt index (I₂), was measured in accordance with ASTM D-1238,condition 190° C./2.16 kg (formally known as “Condition (E)”).

Percent crystallinity is determined by differential scanning calorimetryusing a TA Q10000. The sample was heated to 180° C. and maintained atthat temperature for 3 minutes. It was then cooled at 10° C./min to −90°C. It was then heated at 10° C./min to 150° C. The melting temperaturesand percent crystallinity are reported from the second heat curve. Thepercent crystallinity may be calculated with the equation:percent C=(A/292 J/g)×100,wherein percent C represents the percent crystallinity, and A representsthe heat of fusion of the measured ethylene based polymer in J/g. Themelting point, crystallization point and glass transition temperaturewere also determined by this method.Blend Components

Blend Component 1 is a homogeneous ethylene/alpha olefin copolymerhaving a melt index, I2, of 30 g/10 min and a density of 0.870 g/cm³ asmeasured by ASTM D792 and a melting point as measured by DSC of 65° C.and available from Du Pont Dow Elastomers under the tradename ENGAGE*D8407.

Blend Component 2 is a homogeneous ethylene/octene copolymer having adensity of 0.870 g/cm³ as measured by ASTM D792, and a viscosity of49,000 cP @0 177° C. (350° F.) as measured by the Brookfield ViscosityMethod described herein, and a melting point as measured by DSC of 68°C.

Blend Component 3 is a homogeneous ethylene/octene copolymer having adensity of 0.870 g/cm³ as measured by ASTM D792 and a viscosity of17,000 cP @ 177° C. (350° F.) as measured by the Brookfield ViscosityMethod described herein, and a melting point as measured by DSC of 69°C.

Blend Component 4 is a homogeneous ethylene/octene copolymer having adensity of 0.860 g/cm³ as measured by ASTM D792, and a viscosity of 4170cP @ 177° C. (350° F.) as measured by the Brookfield Viscosity Methoddescribed herein, and a melting point as measured by DSC of 69° C.

Blend component 5 is a PANTHER* 17FB carbon black (a product andtradename of Engineered Carbons).

EPOLENE C-10P is a wax commercially available from Eastman Chemical andhas a viscosity of 4,059 cP @ 177° C. (350° F.) as measured by theBrookfield Viscosity Method described herein, and a melting point asmeasured by DSC of 93° C.

Examples 1-9

A Werner & Pfleiderer ZSK-53 Twin Screw Extruder (TSE) was used toprepare the filled compositions. A water bath and a pelletizer were usedto produce the final product. The composition of the concentratesproduced are shown in Table 1 and their processing conditions aresummarized in Table 2. TABLE 1 Formulations for Carbon Black-FilledCompositions Barium Irganox Total Component 1 Component 2 Component 3Component 5 Stearate 1076 Weight Blend # (wt percent) (wt. percent) (wt.percent) (wt. percent) (phr) (ppm) (lb) Blend 1 50 50 0.05 500 200 Blend2 50 50 0.05 500 200 Blend 3 50 50 0.05 500 200

TABLE 2 Processability of Carbon Black-Filled Compositions Blend percentScrew Speed Throughput Melt Temp. Example # # Torque* (rpm) (lbs/hr)(F.) 1 1 28 200 15 436 2 1 31 250 15 450 3 1 31 300 15 457 4 1 35 200 20468 5 1 37 250 20 468 6 1 34 300 20 502 7 2 23 200 20 453 8 2 24 250 20476 9 2 24 300 20 466 Comp Ex 1 3 45 200 15 500 Comp Ex 2 3 45 200 15561 Comp Ex 3 3 45 250 15 576*Actual Torque = (percent Torque/115)*180

These data show that at the same carbon black loadings, the examples ofthe present invention processed at lower torque and/or lower melttemperatures than those of the Comparative Examples which comprised aresin of comparable density but of a higher molecular weight (and thushigher viscosity) base polymer.

Example 10

A series of experiments were conducted to determine the maximum fillerloading of calcium carbonate (CaC03) and aluminum trihydrate (ATH) inBlend Component 4 in comparison to that of the prior art polymer,Epolene C-10P. The CaCO₃ used was Georgia Marble #9-40 micron and theATH was Alcoa Hydral Alumina H-710-1 micron. The experiments wereconducted in a Haake bowl batch mixer of 69 ml volume. Polymer andfiller which had been dry blended were added to a Haake bowl rotating at30 rpm and preheated to 150° C. The temperature and torque weremonitored until steady state had been reached (generally about fiveminutes of mixing). The resulting mass was recovered, sampled, and usedas a heel for a subsequent blend of higher filler loading. A volume bowlfill of 60 percent (42 cc) gave adequate mixing results.

As each blend was made and removed, approximately 5 grams were saved.The remaining material was weighed and returned to the cleaned rotatingHaake bowl along with any additional constituents (based on requirementsafter calculating the components of the heel) to prepare the next higherfilled sample. Typically the mass could be removed in pieces and balledinto a solid single mass. Occasionally, the resulting blend was flakedor powdered indicating that the blend was not achieved. In this caseeither additional polymer was added lowering the filler level, or alower filler blend was started and increments were lowered to 1 or 2percent increased filler weight. The highest ultimate filler loading wasobserved visually, that is, the last sample at which the blend wouldphysically hold together and not crumble. These data are summarized inTable 3, and indicate that, in the case of both CaCO3 and ATH as filler,much higher ultimate loadings were observed for the compositions of thepresent invention relative to those of the prior art. TABLE 3 HighestUltimate Loading vs Epolene Epolene C-10P Blend Component 4 (4059 cP)(4190 cP) CaCO3 89 wt percent 95 wt percent ATH 77 wt percent 82 wtpercent

Example 11

The complex viscosity of 2 blends at equivalent calcium carbonateloading (89 wt percent) were measured on a Rheometrics RMS-800 with 25mm parallel plates at frequencies up to 100 rad/s at 230° C. in anitrogen purge. The results are summarized in Table 4. TABLE 4Processability of CaCO₃-Filled Compositions at 89 wt percent CaCO₃Loading 11 wt Blend 11 wt percent Frequency Component 4 Epolene C-10Ppercent Viscosity (rad/s) Viscosity (poise) Viscosity (poise) Difference1.58E+00 1.98E+05 2.02E+05 2 2.51E+00 1.22E+05 1.33E+05 8 3.98E+007.64E+04 8.88E+04 14 6.31E+00 4.81E+04 5.90E+04 19 1.00E+01 3.03E+043.90E+04 22 1.59E+01 1.98E+04 2.72E+04 27 2.51E+01 1.30E+04 1.94E+04 333.98E+01 8.92E+03 1.44E+04 38 6.31E+01 6.26E+03 1.08E+04 42 1.00E+024.39E+03 7.95E+03 45

These results again demonstrate that at the higher processing rates ofindustrial interest (100 rad/s), the viscosity of the filled compositionof Blend Component 4 was 45 percent less than that of the the equivalentfilled composition of the prior art, again allowing for better muchbetter processability.

1. A polymer composition comprising a blend of A) and B); A) greaterthan or equal to 40 percent by weight (based on the combined weights ofComponent A and B) of one or more fillers; and B) less than 60 percentby weight (based on the combined weights of Component A and B) of one ormore base polymers; wherein said one or more base polymers is ahomogeneous ethylene/C₃-C₂₀ alpha-olefin interpolymer or a C₃-C₂₀homopolymer or interpolymer, and has 1) a total crystallinity of from 0to 30 percent; and 2) a Brookfield viscosity of from 500 to 50,000 cPmeasured at 350° F. (177° C.).
 2. The polymer composition of claim 1wherein; A) said one or more fillers, Component A, is present in anamount of greater than or equal to 60 percent by weight (based on thecombined weights of Component A and B); and B) said one or more basepolymers, Component B, is present in an amount of less than 40 percentby weight (based on the combined weights of Component A and B); andwherein said base polymer has 1) a total crystallinity of from 3 to 25percent; and 2) a Brookfield viscosity of from 2,000 to 30,000 cPmeasured at 350° F. (177° C.).
 3. The polymer composition of claim 1wherein; A) said one or more fillers, Component A, is present in anamount of greater than or equal to 80 percent by weight (based on thecombined weights of Component A and B); and B) said one or more basepolymers, Component B, is present in an amount of less than 20 percentby weight (based on the combined weights of Component A and B); andwherein said base polymer has 1) a total crystallinity of from 5 to 20percent; and 2) a Brookfield viscosity of from 5,000 to 20,000 cPmeasured at 350° F. (177° C.)
 4. The polymer composition of claim 1wherein; A) said one or more fillers, Component A, is selected from thegroup consisting of glass fibers, talc, calcium carbonate, aluminatrihydrate, glass fibers, marble dust, cement dust, clay, feldspar,silica or glass, fumed silica, alumina, magnesium oxide, magnesiumhydroxide, antimony oxide, zinc oxide, barium sulfate, aluminumsilicate, calcium silicate, titanium dioxide, titanates, glassmicrospheres or chalk, hindered phenolics, phosphites, lightstabilizers,; plasticizers; tackifiers; waxes; processing aids; stearicacid or a metal salt thereof; crosslinking agents; colorants orpigments; carbon black; graphite; carbon fibers; and blowing agents; andany and all combinations thereof; and B) said one or more base polymers,Component B, is a homogeneous ethylene/C₃-C₂₀ alpha-olefin interpolymeror a polypropylene or propylene/C₄-C₂₀ alpha-olefin copolymer.
 5. Thepolymer composition of claim 4 wherein; A) said one or more fillers,Component A, is carbon black; alumina trihydrate, calcium carbonate orany and all combinations thereof; and B) said one or more base polymers,Component B, is a homogeneous ethylene/propylene or ethylene/octene-1copolymer or polypropylene.
 6. The polymer composition of claim 1wherein i) when calcium carbonate is said filler, the highest ultimatefiller loading is greater than 90 weight percent; or ii) when aluminatrihydrate is said filler, the highest ultimate filler loading isgreater than 80 weight percent.
 7. The polymer composition of claim 1wherein B) said one or more base polymers, Component B, is aninterpolymer of ethylene and at least one of propylene; isobutylene;1-butene; 1-pentene; 1-hexene; 3-methyl-1-pentene; 4-methyl-1-pentene;1-hexene and 1-octene.
 8. The polymer composition of claim 7 wherein B)is an interpolymer of ethylene and at least one of: propylene and1-octene.
 9. A polymer composition comprising a filler and polymer,selected from homogeneous ethylene/C₃-C₂₀ alpha-olefin interpolymers orC₃-C₂₀ alpha-olefin homopolymers or interpolymers, characterized in thatwhen said polymer is mixed with calcium carbonate at a concentration of89 weight percent calcium carbonate, the viscosity of the resultingmixture (when measured on a Rheometrics RMS-800 with 25 mm parallelplates at frequency of 100 rad/s at 230° C. in a nitrogen purge) isgreater than 1.3×10⁴ poise.